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1.
Antifouling paint fragments collected from marinas and leisure boat maintenance facilities and in the vicinity of abandoned boats have been chemically characterised. High concentrations of Cu (23-380 mg g−1) and Zn (14-160 mg g−1) in the samples (n = 14) are consistent with the use of these metals in the principal biocidal and non-biocidal pigments in contemporary antifouling formulations. Up to about 2% and 7% of the respective metals were solvent-extractable, suggesting that organo-forms of Cu and Zn (e.g. pyrithiones) were also present. Of the organic biocides, dichlofluanid was present in most samples and at concentrations up to about 20 mg g−1. Chlorothalonil and Irgarol 1051® were only detected in one and four cases, respectively, and Sea Nine 211® was not detected in any sample. Results are discussed in terms of UK legislation regarding biocide usage and the likely effects and fate of discarded paint particles in coastal environments where boats are repaired or moored.  相似文献   

2.
In 2001, legislative measures were introduced in the UK to restrict usage of antifouling agents in small (<25 m) vessel paints to dichlofluanid, zinc pyrithione and zineb. This removed the previously popular booster biocides diuron and Irgarol 1051 from the market. To investigate the impact of this legislation, water samples were taken from locations where previous biocide levels were well documented. Results from analyses demonstrate a clear reduction in water concentrations of Irgarol 1051 (between 10% and 55% of that found during pre-restriction studies), indicating that legislation appears to have been effective. Although other booster biocides were screened for (chlorothalonil, dichlofluanid and Sea-Nine 211), they were below the limits of detection (<1 ng/l) in all samples. A survey of chandlers and discussions with legislative authorities supports these results and concurs the removal of Irgarol 1051 based paints from the market using simple regulations at a manufacturer level with little regulation at a retailer level.  相似文献   

3.
《Marine pollution bulletin》2014,78(1-2):201-208
Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.  相似文献   

4.
The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 μg g−1 of Cu, 475 μg g−1 of Zn, 0.82 μg g−1 of Hg, 94 μg g−1 of Pb and over 10,000 ngSn g−1 of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.  相似文献   

5.
International regulation of organotin compounds for use in antifouling paints has led to the development and increased use of replacement compounds, notably the s-triazine herbicide Irgarol 1051. Little is known about the distribution of Irgarol 1051 in tropical waters. Nor has the potential impact of this triazine upon photosynthesis of endosymbiotic microalgae (zooxanthellae) in corals been assessed. In this study Irgarol 1051 was detected in marinas, harbours and coastal waters of the Florida Keys, Bermuda and St. Croix, with concentrations ranging between 3 and 294 ng 1(-1). 14C incubation experiments with isolated zooxanthellae from the common inshore coral Madracis mirabilis showed no incorporation of H14CO3- from the sea water medium after 4-8 h exposure to Irgarol 1051 concentrations as low as 63 ng 1(-1). Reduction in net photosynthesis of intact corals was found at concentrations of l00 ng 1(-1) with little or no photosynthesis at concentrations exceeding 1000 ng 1(-1) after 2-8 h exposure at all irradiances. The data suggest Irgarol 1051 to be both prevalent in tropical marine ecosystems and a potent inhibitor of coral photosynthesis at environmentally relevant concentrations.  相似文献   

6.
《Marine pollution bulletin》2009,58(6-12):419-424
In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L−1 dissolved in the water, 0.14–6.7 ng (Sn) L−1 in suspended particulate matter and nd ∼ 26 ng (Sn) g−1 (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen’s coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of 210Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.  相似文献   

7.
Effects of new antifouling compounds on the development of sea urchin   总被引：5，自引：0，他引：5  
Tributyltin oxide (TBTO) has been used worldwide in marine antifouling paints as a biocide for some time. However, it produced toxic effects, especially in marine water/sediment ecosystems. Consequently, its use in antifouling paints has been prohibited in many countries. In this study, the toxicity of alternative and/or new antifouling biocides compared with TBTO is assessed by a biological method. The effects of these chemicals on marine species have not been well studied. This paper assesses, comparatively, the effects of eight biocides on sea urchin eggs and embryos. The chemicals assessed were TBTO, Irgarol 1051, M1 (the persistent degradation product of Irgarol), Diuron, zinc pyrithione, 'KH101', 'Sea-Nine 211', and copper pyrithione. For these chemicals, toxicity appears to be in the order zinc pyrithione > Sea-Nine 211 > KH101 > copper pyrithione > TBTO > Diuron approximately = Irgarol 1051 > M1. Here, we show that zinc pyrithione, Sea-Nine 211, KH101, and copper pyrithione are much more toxic to sea urchins than TBTO or the other chemicals.  相似文献   

8.
In the yachting sector of the UK antifouling market, organic biocides are commonly added to antifouling preparations to boost performance. Few data presently exist for concentrations of these compounds in UK waters. In this study the concentrations of tributyltin (TBT) and eight booster biocides were measured before and during the 1998 yachting season. The Crouch Estuary, Essex, Sutton Harbour, Plymouth and Southampton Water were chosen as representative study sites for comparison with previous surveys of TBT concentrations. Diuron and Irgarol 1051 were the only organic booster biocides found at concentrations above the limits of detection. Diuron was measured at the highest concentrations, whilst detectable concentrations of both Irgarol 1051 and diuron were determined in areas of high yachting activity (e.g. mooring areas and marinas). Maximum measured values were 1,421 and 6,740 ng/l, respectively. Lower concentrations of both compounds were found in open estuarine areas, although non-antifouling contributions of diuron may contribute to the overall inputs to estuarine systems. TBT was found to be below or near the environmental quality standard (EQS) of 2 ng/l for all samples collected from estuarine areas frequented by pleasure craft alone, but with much higher concentrations measured in some marinas, harbours and in areas frequented by large commercial vessels. Using the limited published environmental fate and toxicity data available for antifouling booster biocides, a comparative assessment to evaluate the risk posed by these compounds to the aquatic environment is described. TBT still exceeds risk quotients by the greatest margins, but widespread effects due to Irgarol 1051 and less so diuron cannot be ruled out (particularly if use patterns change) and more information is required to provide a robust risk assessment.  相似文献   

9.
A study of the distribution of the 'booster' biocide 2-methylthio-4-tert-butylamino-6-cyclopropyl amino-s-triazine (Irgarol 1051) was carried out in the coastal waters of Bermuda. Irgarol 1051 concentrations (as determined by GC/MS) up to 590 ng l-1 have been measured within Hamilton Harbour. The data presented herein unequivocally demonstrate contamination of the coastal system of Bermuda by Irgarol 1051. Concurrently, TBT concentrations were measured and results indicate that levels are falling through legislated changes in antifouling treatments, from 220 ng l-1 in 1990 to < 20 ng l-1 (as Sn) by 1995, in the open water area of Hamilton Harbour. Concentrations of TBT immediately offshore from a boatyard were found to be > 600 ng l-1 (Sn), indicating continuing release due to painting operations and sediments in the area.  相似文献   

10.
《Marine pollution bulletin》2013,70(1-2):189-194
Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol’s metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms.  相似文献   

11.
Water and surface sediment samples were analyzed for butyltins (TBT, DBT, MBT) from various ports along the east and west coast of India. The total butyltin (TB) in water samples varied between ∼1.7 and 342 ng Sn l−1, whereas for sediments it varied between below detection limit to 14861 ng Sn g−1 dry weight of sediment. On an average Chennai port recorded the highest level of butyltins in the sediments while Paradip recorded the highest level of butylins in the waters. A fairly good relationship between the TB in the sediment and overlying water samples, as well as between organic carbon and TB, implicates the importance of adsorption/desorption process in controlling the levels of TBT in these port areas. In India the data on organotin pollution is very sparse; most of the port areas have been surveyed for butyltins for the first time during this study.  相似文献   

12.
Irgarol 1051 is a s-triazine herbicide used in popular slime-resistant antifouling paints. It has been shown to be acutely toxic to corals, mangroves and sea grasses, inhibiting photosynthesis at low concentrations (>50 ng l(-1)). We present the first data describing the occurrence of Irgarol 1051 in coastal waters of the Northeastern Caribbean (Puerto Rico (PR) and the US Virgin Islands (USVI)). Low level contamination of coastal waters by Irgarol 1051 is reported, the herbicide being present in 85% of the 31 sites sampled. It was not detected in water from two oceanic reference sites. In general, Irgarol 1051was present at concentrations below 100 ng l(-1), although far higher concentrations were reported at three locations within Benner Bay, USVI (223-1,300 ng l(-1)). The known toxicity of Irgarol 1051 to corals and sea grasses and our findings of significant contamination of the Northeastern Caribbean marine environment by this herbicide underscore the importance of understanding, more fully, local and regional exposure of reef and sea grass habitats to Irgarol 1051 and, where necessary, implementing actions to ensure adequate protection of these important ecosystems.  相似文献   

13.
Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g−1, as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g−1, as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content).  相似文献   

14.
The presence of booster biocides in the aquatic environment has been associated with a risk to non-target species due to their proven toxicity. The aim of the present study was to determine the spatial and temporal distribution of common booster biocides in different harbours of the island of Gran Canaria (Spain) and evaluate, by means of a probabilistic risk assessment (PRA), the ecological risk posed by these compounds. With these objectives, a monitoring campaign was conducted between January 2008 and May 2009, collecting a total of 182 seawater samples. Four common booster biocides (TCMTB, diuron, Irgarol 1051 and dichlofluanid) were monitored. Diuron levels ranged between 2.3 and 203 ng/L and Irgarol 1051 between 2.4 and 146.5 ng/L. The ecological risk associated with these levels was always low, however, with probabilities of exceeding the 10th percentile of autotroph toxicity below 3.5%.  相似文献   

15.
Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g−1, respectively, and small proportions of these metals (<2%) in organometallic form as pyrithione compounds. Other trace metals present included Ag, Cd, Cr, Ni, Pb and Sn, with maximum concentrations of about 330, 75, 1200, 780, 1800 and 25,000 μg g−1, respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in “background” sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.  相似文献   

16.
Organotins, especially tributyltins (TBT) are highly toxic to many marine organisms. These compounds are introduced in marine waters by ship trafficking, ship scrapping activities, as antifouling compounds and sewage disposal. Marine fishes, crustaceans and molluscans are easily prone to organotins contamination. In view of this, a baseline monitoring study was conducted in order to establish the levels of organotins in edible marine fishes, bivalves, shrimps, squids and crabs collected from Mumbai, Goa and Karwar on the west coast of India. At these locations average organotin concentration found in fishes, clams, shrimps, squids and crabs was 108, 852, 179, 70 and 89 ng Sn g−1 dw, respectively. In all the samples butyltins dominated over phenyltins. The levels of organotins suggest that all the organisms were contaminated with organotins and their consumption may pose health problems to humans.  相似文献   

17.
《Marine pollution bulletin》2009,58(6-12):575-586
Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an algaecide commonly used in antifouling paints. It undergoes photodegradation which yields M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) as its major and most stable degradant. Elevated levels of both Irgarol and M1 have been detected in coastal waters worldwide; however, ecotoxicity effects of M1 to various marine autotrophs such as cyanobacteria are still largely unknown. This study firstly examined and compared the 96 h toxicities of Irgarol and M1 to the cyanobacterium Chroococcus minor and two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana. Our results suggested that Irgarol was consistently more toxic to all of the three species than M1 (96 h EC50 values: C. minor, 7.71 μg L−1 Irgarol vs. >200 μg L−1 M1; S. costatum, 0.29 μg L−1 Irgarol vs. 11.32 μg L−1 M1; and T. pseudonana, 0.41 μg L−1 Irgarol vs. 16.50 μg L−1 M1). Secondly, we conducted a meta-analysis of currently available data on toxicities of Irgarol and M1 to both freshwater and marine primary producers based on species sensitivity distributions (SSDs). Interestingly, freshwater autotrophs are more sensitive to Irgarol than their marine counterparts. For marine autotrophs, microalgae are generally more sensitive to Irgarol than macroalgae and cyanobacteria. With very limited available data on M1 (i.e. five species), M1 might be less toxic than Irgarol; nonetheless this finding warrants further confirmation with additional data on other autotrophic species.  相似文献   

18.
The kinetics of the photoinduced degradation and transformation of the antifouling booster biocide, Irgarol-1051, in natural coastal seawater was studied. The measured first-order rate constant for the degradation of Irgarol-1051 was 4.02 ± 0.1 × 10−4 h−1, while the rate constant for the formation of 2-methylthio-4-tert-butylamino-6-amino-s-triazine (M1), the most dominant degradation product of Irgarol-1051, was 4.6 ± 0.1 × 10−5 h−1. This considerably slower rate suggested that the transformation of Irgarol-1051 to M1 may not be the predominant pathway of the photodegradation process. During the photodegradation study, a new s-triazine species was observed in the degradation mixtures which, together with M1, appeared immediately upon photolysis and continued to accumulate in the degradation mixture throughout the entire study duration. This is in contrast to the behaviour of the recently identified degradation product of Irgarol-1051, 3-[4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]- propionaldehyde (M2), which was only detected in the degradation mixture after a long induction period. High-resolution tandem mass spectrometric analysis hinted that the new degradation product (M4) may possess a terminal alcohol and is likely to be an N-allylic alcohol derivative of M1. This suggests that M4 may, indeed, be a precursor of M2 via redox transformation at its N-allylic alcohol functionality.  相似文献   

19.
In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L(-1) dissolved in the water, 0.14-6.7 ng (Sn) L(-1) in suspended particulate matter and nd approximately 26 ng (Sn) g(-1) (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen's coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of (210)Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.  相似文献   

20.
The International Maritime Organisation's (IMO) ban on the use of tributyltin in antifouling paints has inevitability increased the use of old fashioned antifoulants and/or the development of new paints containing 'booster biocides'. These newer paints are intended to be environmentally less harmful, however the broader environmental effects of these 'booster biocides' are poorly known. Germination and growth inhibition tests using the marine macroalga, Hormosira banksii (Turner) Desicaine were conducted to evaluate the toxicity of four new antifouling biocides in relation to tributyltin-oxide (TBTO). Each of the biocides significantly inhibited germination and growth of Hormosira banksii spores. Toxicity was in increasing order: diuron < zineb < seanine 211< zinc pyrithione < TBTO. However, the lack of knowledge on partitioning in the environment makes it difficult to make a full assessment on whether the four biocides tested offer an advantage over organotin paints in terms of environmental impact.  相似文献   

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